Catalytic reforming



Patented Mar. 6, 1945 CATALYTIC REFORMING Charles L. Thomas and Jacob Elston Ahlberg, Chicago, 11]., assig'nora to Universal Oil Prodnets Company, Chicago, 11]., a corporation of Delaware No Drawing. Application March'31, 1941,

Serial No. 386,123

3 Claims.

This application is a continuation-in-part of our co-pending application Serial No. 288,579, filed August 5, 1939, which was a continuationin-part of our application Serial No. 236,549, filed October 22, 1938, now Patent No. 2,285,314, granted June 2, 1942. v

This invention relates to the use of catalysts for accelerating reactions among hydrocarbons, and more specifically, it has reference to a method for selectively promoting reforming of gasoline fractions obtained in thermal cracking and thermal reforming by means of particularly effective refractory catalytic materials characterized by their method of manufacture. I

The present invention involves a conversion of olefinic hydrocarbons in the presence of specific catalytic materials which function to selectively isomerize said olefinie hydrocarbons with the resulting increase in the octane number of the motor fue1s.- The composition of the gasoline fractions obtained in thermal cracking and thermal reforming is quite complex. It cannot be stated with certainty what reactions areresponsible for the increase in the octane number when these charging stocks are subjected to the action of a catalyst the preparation of which is hereinafter described. These preferred catalysts are characterized in their effectiveness in isomerizing olefins and in promoting the other reactions which cause an improvement in the motor fuel characteristics of the charging stock with the simultaneous formation of a minimum quantity of carbonaceous deposit, heavy polymers, as well as normally gaseous products. These catalysts are also characterized by their refractory properties'which enable them to withstand severe conditions of temperature and pressure to which they are subjected and are further characterized by their ease and simplicity of manufacture and their exact reproducibility.

In one specific embodiment, the present; invention comprises the use of catalysts suitable for use in reforming olefinic gasolines, the catalytic material being made by preparing in the primary step a precipitated hydrated silica gel, treating and washing said silica gel with a reactant and water to effect substantially complete removal of alkali metal ions, suspending the purified precipitated silica in a solution of an aluminum salt, removing excess liquid and drying of the composite to remove a major portion of the water content, forming into particles of the desired sizes and calcining the purified catalytic material.

Generally speaking, a purified silica gel is added to a solution of an aluminum salt and the alumina precipitated by hydrolysis, preferably by heating,

or the purified silica gel may be thoroughly admixed with a solution of an aluminum salt and and selective in reforming oleflnic gasolines when.

heated, whereby alumina will be deposited by the decomposition of said aluminum salt.

We have found that the silica and alumina catalyst which may be prepared by the several alternative methods described in detail in the following paragraphs, are rendered more stable over long periods of use and are also more active the originally precipitated hydrated silica. which forms a primary material upon which the precipitated alumina is subsequently deposited is substantially freed from alkali metal ions. These alkali metal ions will in the more general methods of preparation be sodium ions inasmuch as the various sodium silicates comprise one of the more readily available raw materials for the manufacture of this type of catalyst. A purification treatment which constitutes one of the main features of our invention is described in detail in one of the later paragraphs. The characteristics and efficiency of the final alumina and silica catalysts will vary more or less in the exact condition of precipitation and/or purification treatment and the ratio of silica to alumina.

In the catalysts thus prepared the ratio of silica to alumina by weight may range from 1 to 1 to 10 to 1 or greater ratios may be used, active catalysts having been prepared in which the ratio is as high as 50 to 1 so that in effect the alumina may be considered to act as a promoter of the catalytic activity of the silica. It is to be recognized that very little is known positively concerning the mechanism of promoter action in catalysis and no attempt will be made herein to offer any definite reason for the observed effect of the addition of varying amounts of alumina to silica. There may be a joint promoter effect or it may be that the alumina is the more active catalyst and is extensively dispersed in and on the silica in order to present a large surface;

An important feature of our invention-resides in the fact that catalysts of greatly increased stability and efficiency in the reforming reactions are produced when there is substantially complete exclusion of alkali metal ions from the hydrated alumina-silica masses prior to their drying and calcining to; prepare them for service. In the present invention a precipitated hydrated, silica gel substantially free from alkali metal ions is used as the primary material or base-for the subsequent'deposition of hydrated alumina. Silica gel free from alkali metal ions may be prepared by the hydrolysis of silicon tetrachloride, for example, but in the more usual method the hydrated silica gel will be prepared by the acidification of alkali metal silicates, whereby alkali metal ions are unavoidably incorporated into the silica gel which are removed as one feature in the process of our invention. 'It is not positively known whether the alkali metal compounds, such as those of sodium, are present in chemical combination or in an adsorbed state, but it has been definitely determined that their exclusion or removal is necessary if catalysts of superior activity and stability are to be obtained. It may be cons'idered that the presence of these alkali metal ions may cause a sintering or fusion of the surfaces of the primary composites of the catalytic material at elevated temperatures so that the porosity of the catalyst particles is reduced or altered with a corresponding reduction in effective surface considering the catalytic eflects to be due at least in part to surface action. However. such concepts are principally speculative in view of the difiiculty of obtaining direct confirmatory evidence.

Several alternative purification methods are applicable to primary hydrated silica gels prepared by the acidification of alkali metal silicate solutions to insure the substantially complete absence of sodium or other alkali metal silicatesolutions to insure the substantially complete absence of sodium or other alkali metal ions. .One-

method consists in treating and washing the precipitated silica gel with acidic solutions to extract alkali metal impurities incorporatedinto the silica gel'during its preparation bythe formation of corresponding alkali metal salts. Thus a precipitated silica gel may be first washed with water to remove a major portion of the soluble impurities and subsequently treated with a mineral acid, for example, such as hydrochloric acid and water to remove the alkali metal ions. As an alternative purification method the primary precipitated hydrated silica may be treated with ammonium compounds of salts, such' as ammonium chloride in solution or other halides, the sulfate, the nitrate,'the phosphates, or the acetate, so that alkali metal ions will not be substantially present in the primary gel when it has been suitably washed. Whether the alkali metal ions are present in the hydrated silica gel in a chemically combined or adsorbed condition, the alkali metal ions may be replaced by the ammonium ions which will be later expelled from combination or adsorption in subsequent treatment at elevated temperature.

Another alternative method for removing al kali metal ions from the precipitated hydrated silica gel consists in treating with salts of multivalent metals which may replace the sodium or other alkali metals in the manner similar to that present invention to form catalysts suitable for hydrocarbon reactions.

The weight of evidence at hand on the mechanism leading to the replacement of alkali metals in the primary hydrated gel indicates that the alkali metals are held byadsorptionv rather than by chemical bonds. This'is indicated by the fact that the alkali metal ions are replaceable by ammonium or multivalent positive ions which are known in general to be more strongly adsorbed than alkali metal ions. This differentiates this replacement from the base exchange that occurs inthe case of zeolites. 7

After the alumina has been mixed or deposited upon the purified hydrated silica gel and water washed, if desired, it may be recovered as a filter cake and dried at a temperature of the order of 240-300 F., more or less, after which it may be pressed and sized to recover particles of a convenient average size or formed into desired shapes by compression methods. It has been found that after the usual drying treatment the material usually has a total water content of approximately 15 per cent which appearsto correspond to the best workability of the material. By calcinin the particles at temperatures of the order of 850- 1000 F., or higher, maximum activity of the catalyst is obtained and a further dehydration occurs so that, for example, after a period of heating at 900 F. the water content as determined by analysis is of the order of 2 to 3 per cent which does not vary appreciably either as the result of long service or a large number of reactivations at considerably higher temperatures.

Catalysts prepared by theuabove general procedure evidently possess a large total contact surface corresponding to a high porosity, the pores being of such size that hydrocarbon oil vapors are able to penetrate to a considerable distance and yet not so small that when the pores become clogged with carbonaceous deposits after a long,

period of service, they are difficult to reactivate by oxidation. This structure is also retained after described in the case of ammonium compounds.

For example, a primary gel having large amounts of alkali metal compounds present may be treated with a solution of salts of multivalent metals. more particulary aluminum, in which the metal forms the positive ion of the salt being used. In.

this mode of operation the multivalent used to many alternate periods of use and reactivation as evidenced by the fact that the catalyst may be repeatedly reactivated by passing air or other oxidizing gas over the spent particles to burn on deposits of carbonaceous material at temperatures as high as 1400 to 1600 F. without material loss of catalytic activity.

According to the present process catalysts prepared by the general procedure described in the preceding paragraphs, may be employed as filling material in .tubes or chambers in the form of small pellets or granules. In the example given below, the average particle size was within the range of 6 to 10 mesh. These particles may be formed by pilling, briquetting, or extruding, the pilling probably being the preferred method of forming the granules.

The general procedure adopted for the reforming process involves contacting the heated gasoline fraction with the catalyst with the subsequent separation of the small quantities of nor-' space velocity depending upon the temperature being used. Pressures which range from atmospheric to as much as 50 or 100 pounds per square inch may be used. As the pressure isincreased, the amount of heavy bottoms formed increases and a preferred method of operation appears to be to simply use a sufliciently high pressure to cause the'materials to flow readily through the catalyst bed and into the subsequent separating equipment. When utilizing 'pressures approximately'atmospheric and temperatures of 950 F.,

space velocities within the range of to 25 voltunes of liquid charging stock per hour per unit volume of catalyst, may be used. As the temperature is increased, the space velocities must be increased. For example, at a temperature of 1030 F. a space velocity of 80 may besatisfactorily used.

The following example of preparation of catalyst peculiar to the present invention is given I to indicate its novelty and utility although not for the purpose of limiting said invention in the exact agreement with the data introduced.

390 cc. of concentrated hydrochloric acid in 1815 cc. of solution was added to 568.4 grams of sodium silicate (NazSiOa.9I-Iz0) in 300 cc. of water which gave a liquid suspension which was definitely acidic to blue litmus. The filter cake was then slurried in 2 /2 liters of water and 111- tered, this washing treatment being repeated several times. The, filter cake was slurried in 2 liters of water after which $4; equivalent of hydrochloric acid in 50 cc. of water was-added. The precipitate was filteredand this treatment again repeated. The filter cake was slurried in water and water washing treatment repeated 4 times when the wash waterfwas practically free from alkali metal salts. The purified silica was then slurried in 40.24 grams of aluminum chloride hexahydrate dissolved in 400 cc. of water. The

excess liquid was then drained by filtration and the filter cake dried at approximately 800 F.

The dried material was then pressed and sized into 6-10 mesh particles and subsequently calcined at approximately 932 F.

A charging stock comprising a gasoline obtained by thermally cracking a Pennsylvania gas oil and having the following characteristics, was

used as a charge in the reforming operation.

Charging stock (thermally cracked gasoline) a. P. re. ace

Utilizing a catalyst prepared bythe above method, a. yield of.9'7.8 per cent of reformed gasoline having an octane number of 72.9 A. S. 'I. M. motor method, may be obtained when operating at a temperature of 955 F. at aliquid hourly space velocity corresponding to 15.1 volumes of liquid charging stock per hour per unit volume of catalyst.

We claim as our invention:

1. A process for increasing the octane number of an olefinic gasoline fraction resulting from the thermal conversion of hydrocarbon oil which comprises subjecting said gasoline fraction at a temperature of from 800 to about 1100 F., a pressure of from atmospheric to about 100 pounds per square inch and for a time of contact corresponding to a liquid hourly space velocity of from 5 to about volumes of liquid per unit volume of catalyst to the action of a catalyst prepared by precipitating a silica hydrogel from a solution of an alkali metal silicate by acidification thereof, suspending the hydrogel in a solution of an aluminum salt and precipitating alumina by hydrolysis upon said suspended silica hydrogel, washing the precipitated material and heating to remove a major portion of its water content, and

calcining above a temperature of about 850 F. Y a

2. A process for increasing the octane number of an oleflnic gasoline fraction resulting from the thermal conversion of hydrocarbon oil which ajliquid hourly space velocity of from 5 to about 25 volumes of liquid per unit volume of catalyst;

to contact with a catalyst prepared by commingling a silica hydrogel and a solution of an aluminum salt, precipitating alumina from said solution upon the silica hydrogel by hydrolysis of the aluminum salt, and drying the resultant silicaalumina composite.

3. A process for reforming an olefinic gasoline fraction which comprises subjecting said fraction resulting from the thermal conversion of hydrocarbon oil at a temperature within the approximate limits of 800 to 1100 F. and at a pressure of from substantially atmospheric to about pounds per square inch and for a time of contact corresponding to a space velocity of about 5 to about 25 volumes of liquid per hour per unit volume of catalyst, to the action of a catalyst prepared by the hydrolytic absorption of alumina on a precipitated silica hydrogel, said composite having been substantially freed of alkali metal compounds, dried sufliciently to permit forming into particles of the desired size, and calcined above a temperature of about 850 F.

CHARLES L. THOMAS. JACOB ELSTON AIILBERJG. 

